Physical vapor deposition apparatus and physical vapor deposition method

ABSTRACT

A physical vapor deposition apparatus and a physical vapor deposition method for forming a film of a substance which is hard to be made fine particles even when it is heated by plasma, arc discharge, or the like are provided. It has an evaporation chamber  10  provided inside it with an evaporation source material  15  and a heating part  16  for heating the evaporation source material  15 , a powder supply source  20  provided inside it with a powder, and a film forming chamber  30 , wherein the evaporation source material  15  is heated by the heating part  16  to produce fine particles (nanoparticles), the fine particles and powder are sprayed out of a supersonic nozzle  35 , are placed on a supersonic gas stream, and are deposited on a substrate for film formation  33  by physical vapor deposition.

TECHNICAL FIELD

The present invention relates to a physical vapor deposition apparatusand a physical vapor deposition method, more particularly relates to aphysical vapor deposition apparatus which mixes fine particles producedby atoms which have been evaporated from an evaporation source materialwith a powder and deposits the result on a substrate for film formationand to physical vapor deposition method of the same.

BACKGROUND ART

In recent years, coating technology has been rapidly rising inimportance. Various coating methods are being developed.

However, a coating method capable of constructing a high density coatingfilm having a thickness of about tens to hundreds of micrometers has notbeen known.

The document A. Yumoto, F. Hiroki, I. Shiota, N. Niwa, Surface andCoatings Technology, 169-170, 2003, 499 to 503 and the document AtsushiYumoto, Fujio Hiroki, Ichiro Shiota, Naotake Niwa, Formation of Ti andAl Films by Supersonic Free Jet PVD, The Journal of the Japan Instituteof Metals, Vol. 65, No. 7 (2001) pp. 635 to 643 disclose supersonic freejet (SFJ) physical vapor deposition (PVD) apparatuses.

Such an SFJ-PVD apparatus is provided with an evaporation chamber and afilm forming chamber.

In the evaporation chamber, an evaporation source material which is seton a hearth which is cooled by water and an electrode which is made of ahigh melting point metal (specifically tungsten) are provided. Theinterior of the evaporation chamber is once reduced to a predeterminedpressure then the atmosphere is substituted with a predetermined gasatmosphere. Using the evaporation source material as an anode and a highconductive metal which is located at a position which is spaced from theanode with a constant distance as a cathode, a negative voltage and apositive voltage are applied to induce an arc discharge between the twoelectrodes. Due to this transfer type arc plasma, the evaporation sourcematerial is heated and evaporated. In an evaporation chamber made apredetermined gas atmosphere, atoms which are evaporated by heating ofthe evaporation source material agglomerate with each other whereby fineparticles having sizes of the nanometer order (hereinafter referred toas “nanoparticles”) are obtained.

The obtained nanoparticles ride a gas flow induced due to a pressuredifference (difference of degree of vacuum) between the evaporationchamber and the film forming chamber so as to be transported through atransport pipe to the film forming chamber. In the film forming chamber,a substrate for film formation is provided.

The gas flow due to the pressure difference is accelerated up to asupersonic speed of about Mach 3.6 by a specially designed supersonicnozzle (Laval nozzle) which is attached to a front end of the transportpipe connected from the evaporation chamber to the film forming chamber.The nanoparticles ride the air current of the supersonic free jet andare accelerated to a high speed and sprayed to the film forming chamberto be deposited on the substrate for film formation.

By using the SFJ-PVD apparatus described above, it becomes possible toconstruct a high density coating film having tens to hundreds ofmicrometers of thickness at a low temperature.

Here, the object of forming a film on the surface of the film formationobject is the protection of the surface of the film formation object,insulation of the film formation object, and so on. It has been desiredthat the material for forming the film have characteristics such asexcellent heat resistance, chemical stability, and toughness.

Accordingly, in order to improve the above characteristics of the filmwhich is formed on the surface of the film formation object, forexample, there is known the physical vapor deposition apparatusdisclosed in Japanese Patent Publication (A) No. 2006-111921 whereinfirst fine particles and second fine particles are produced in twoevaporation chambers, are mixed by utilizing an oscillation phenomenonof coaxial impinging jets described in the document Keijiro Yamamoto,Akira Nomoto, Tadao Kawashima, and Nobuaki Nakaji, OscillationPhenomenon of Coaxial Impinging Jets, Hydraulics and Pneumatics (1975)pp. 68 to 77, and are made to ride on a supersonic gas flow to be madeto deposit on the substrate by physical vapor deposition.

DISCLOSURE OF INVENTION Technical Problem

However, a material which is excellent in heat resistance and ischemically stable is hard to evaporate, therefore film formation by thevapor deposition method was difficult in comparison with the othermaterials. For example, a substance, like a ceramic, which has heatresistance is hard to be made into fine particles even when it is heatedby plasma, arc discharge, or the like. Film formation of such asubstance by plasma, arc discharge, etc. is difficult in comparison withother materials. Further, ceramic by nature has a weak adhesive power toa substrate, is easily peeled off, is brittle, and is easily broken whenit is formed on a substrate as a thin film. A stable film could not beformed.

Accordingly, an object of the present invention is to provide a physicalvapor deposition apparatus and a physical vapor deposition method forformation of a film of a substance which is hard to form into fineparticles even when it is heated by plasma, arc discharge, or the like.

Further, an object is to provide a physical vapor deposition apparatusand a physical vapor deposition method for mixing a material, whichwould exhibit brittleness if it were used solo to form a film, withanother material so as to form a film.

Further, an object is to provide an inexpensive physical vapordeposition apparatus and physical vapor deposition method which enablesfilm formation without the use of a plurality of vacuum vessels andheating devices when mixing a plurality of materials to form a film.

Technical Solution

A physical vapor deposition apparatus of the present invention includes:an evaporation chamber which is provided inside therein with anevaporation source material and a heating part for heating theevaporation source material, which heats the evaporation source materialby the heating part under a predetermined gas atmosphere or airatmosphere to evaporate it, and which produces fine particles fromevaporated atoms; a powder supply source which is provided insidethereof with a powder; and a film forming chamber which is providedinside thereof with a mixing part which is connected to transport pipeswhich form paths for transporting a gas which contains the fineparticles from the evaporation chamber and for transporting a gascontaining the powder from the powder supply source and which mixes thefine particles and the powder, a supersonic nozzle which is connected tothe mixing part, and a substrate for film formation, which makes thefine particles and the powder transported from the evaporation chamberand the powder supply source ride an a supersonic gas stream created bythe supersonic nozzle, and which deposits the fine particles and thepowder on the substrate for film formation by physical vapor deposition.

The above physical vapor deposition apparatus of the present inventionpreferably uses fine particles made of metal as the fine particles anduses a powder made of ceramic as the powder.

Further, the physical vapor deposition method of the present inventiondescribed above includes: a production step of heating and evaporatingan evaporation source material in a predetermined gas atmosphere or theair atmosphere by a heating part which evaporates the evaporation sourcematerial to produce fine particles from evaporated atoms, a mixing stepof transporting the fine particles and the powder from the powder supplysource to a mixing part and mixing the fine particles and the powder inthe mixing part, and a film forming step of making the mixed fineparticles and powder ride a supersonic gas stream created by asupersonic nozzle connected to the mixing part, depositing this on thesubstrate for film formation by physical vapor deposition, and forming afilm containing the fine particles and the powder.

The above physical vapor deposition method of the present inventionpreferably uses fine particles made of metal as the fine particles anduses a powder made of ceramic as the powder.

Further, a physical vapor deposition apparatus of the present inventionincludes: an evaporation chamber which is provided inside thereof withan evaporation source material and a heating part for heating theevaporation source material, which heats the evaporation source materialby the heating part under a predetermined gas atmosphere or airatmosphere to evaporate the same, and which produces fine particles fromevaporated atoms; a powder supply source which is provided insidethereof with a powder; and a film forming chamber which is providedinside thereof with a first supersonic nozzle which is connected to atransport pipe which forms a path for transporting a gas containing thefine particles from the evaporation chamber, a second supersonic nozzlewhich is connected to a transport pipe which forms a path fortransporting a gas containing the powder from the powder supply source,and a substrate for film formation, which makes the fine particles whichwere transported from the evaporation chamber ride a supersonic gasstream which is created by the first supersonic nozzle, which makes thepowder which was transported from the powder supply source ride asupersonic gas stream which is created by the second supersonic nozzle,and which deposits the fine particles and the powder on the substratefor film formation by physical vapor deposition.

The above physical vapor deposition apparatus of the present inventionpreferably uses fine particles made of metal as the fine particles anduses a powder made of ceramic as the powder.

Further, the physical vapor deposition method of the present inventiondescribed shove includes: a production step of heating and evaporatingan evaporation source material in as predetermined gas atmosphere or theair atmosphere by a heating part for evaporating the evaporation sourcematerial and producing fine particles from evaporated atoms and a filmforming step of transporting the fine particles and placing these on asupersonic gas stream created by a supersonic nozzle, transporting thepowder from the powder supply source and placing it on a supersonic gasstream created by a supersonic nozzle different from the previouslydescribed supersonic nozzle, and depositing the fine particles an thepowder on a substrate for film formation by physical vapor deposition toform a it containing the fine particles and the powder.

Advantageous Effects

According to the present invention, there is provided a physical vapordeposition apparatus and a physical vapor deposition method, for forminga film of a substance which is hard to be made into fine particles evenwhen it is heated by plasma, arc discharge, the like.

Further, according to the present invention, there can be provided aphysical vapor deposition apparatus and a physical vapor depositionmethod, for forming a film by mixing a substance, which would exhibitbrittleness if it were used solo to form a film, with another substance.

Further, according to the present invention, there can be provided aninexpensive physical vapor deposition apparatus and physical vapordeposition method, capable of forming a film without using a pluralityof vacuum vessels and heating devices when a film is formed by mixing aplurality of materials.

BRIEF DESCRIPTION OF DRAWINGS

[FIG. 1] FIG. 1 is a schematic view of the configuration of a physicalvapor deposition apparatus according to a first embodiment of thepresent invention.

[FIG. 2] FIG. 2 is a view showing an arc torch which configures part ofthe physical vapor deposition apparatus according to the firstembodiment of the present invention.

[FIG. 3] FIG. 3 is a schematic view of a mixing device which utilizes anoscillation phenomenon of coaxial impinging jets in the first embodimentof the present invention.

[FIG. 4] FIG. 4 is a flow of a physical vapor deposition method in thefirst embodiment of the present invention.

[FIG. 5] FIG. 5 is a cross-sectional view showing a cross-section of afilm manufactured by the physical vapor deposition apparatus in thefirst embodiment of the present invention.

[FIG. 6] FIG. 6 is a schematic view of the configuration of a supersonicfree jet physical vapor deposition apparatus for forming a metal film inwhich hydroxyapatite particles are dispersed according to a secondembodiment of the present invention.

[FIG. 7] FIG. 7 is a flow of a physical vapor deposition method in thesecond embodiment of the present invention.

[FIG. 8] FIG. 8A and FIG. 8B are electron micrographs according toExample 1.

[FIG. 9] FIG. 9A and FIG. 9B are X-ray diffraction profiles according toExample 2.

[FIG. 10] FIG. 10A to FIG. 10D are electron micrographs according toExample 3.

EXPLANATION OF REFERENCES

10 . . . evaporation chamber, 11 . . . exhaust pipe, 12 . . . mass flowcontrol, 13 . . . gas supply source, 14 . . . crucible, 15 . . .evaporation source material, 16 . . . heating part, 17, 27 . . .transport pipes, 20 . . . powder supply source, 30 . . . film formingchamber, 31 . . . exhaust pipe, 32 . . . stage, 33 . . . substrate forfilm formation, 34 . . . mixing part, 35, 36, 37 . . . supersonicnozzles, 50 . . . arc torch, 51 . . . torch electrode, 60 . . . binder,61 . . . powder, 70 . . . first mixing nozzle, 71 . . . first extrusionport, 72 . . . first jet, 80 . . . second mixing nozzle, 81 . . . secondextrusion port, 82 . . . jet, 90, 91 . . . partition plates, 92, 93 . .. opening portions, 94, 95 . . . mixed fluids, 96 . . . merged fluid,100 . . . powder, 101 . . . fine particle material film, ARC . . . arc,T1 . . . first fluid supply tube, T2 . . . second fluid supply tube,VP1, VP2, VP3 . . . vacuum pumps, MR . . . mixing region, and J, J1, J2. . . air currents of supersonic free jets.

Best Mode for Carrying out the Invention

Embodiments of a physical vapor deposition apparatus according to thepresent invention will be explained with reference to the drawings.

First Embodiment

FIG. 1 is a schematic view of the configuration of a physical vapordeposition (PVD) apparatus according to the present embodiment comprisedof an SFJ-PVD apparatus.

The PVD apparatus of the present embodiment is provided with anevaporation chamber 10, a powder supply source 20, and a vacuum chamberfor film formation comprised of a film forming chamber 30.

In the evaporation chamber 10, an exhaust pipe 11 connected to a vacuumpump VP1 is provided. The interior of the first evaporation chamber 10is evacuated by operation of the vacuum pump V1 and is made anultra-high vacuum atmosphere of for example about 10-10 Torr. Further,according to need, He, N2, or another inert gas is supplied into theevaporation chamber 10 with a predetermined flow rate from a gas supplysource 13 which is provided at the evaporation chamber 10 through a massflow controller 12. Alternatively, the interior may be made airatmosphere as well.

In the evaporation chamber 10, a copper crucible 14 which is cooled bywater is provided. In this, an evaporation source material 15 ischarged. In the vicinity of the evaporation source material 15, aheating part 16 for heating the evaporation source material 15 isprovided. The evaporation source material 15 is heated by the heatingpart 15 to evaporate, whereby fine particles which have sizes of thenanometer order (hereinafter, also referred to as “nanoparticles”) areobtained from atoms which are evaporated from the evaporation sourcematerial 15.

The obtained nanoparticles are transported together with the atmosphericgas in the evaporation chamber 10 through a transport pipe 17 to thefilm forming chamber 30.

In the powder supply source 20, a powdery material (hereinafter, alsoreferred to as a powder) is contained. The pressure inside the vesselwhich configures part of the powder supply source 20 is not particularlylimited, but preferably the pressure is made that of the air atmospherefrom a viewpoint of operability.

A commercially available powder material can be used as the abovepowder. The powder has a particle size of for example not more thanseveral tens of micrometers, preferably, for example, about 5 to 10 μm.

Then, the powder is stirred up in the vessel by for example making thevessel of the powder supply source 20 vibrate. The stirred up powder istransported together with the inert gas in the vessel to the filmforming chamber 30 through the transport pipe 27.

In the film forming chamber 30, an exhaust pipe 31 connected to a vacuumpump VP3 is provided. The interior or the film forming chamber 30 isevacuated by operation of the vacuum pump V3 and is made an ultra-highvacuum atmosphere of for example about 10-10 Torr.

In the film forming chamber 30, a stage 32 driven in an X-Y direction isprovided. A substrate for film formation 33 is fixed on this stage 32.

The substrate for film formation is not particularly limited. However,use can be made of for example a pure titanium sheet (JIS grade 1),A1050 aluminum alloy sheet, and SUS304 stainless steel sheet. Thesubstrate for film formation is preferably used after cleansing bysupersonic waves in acetone before setting in the film forming chamber.

A mixing part 34 is provided at a merged portion of the front end of thetransport pipe 17 from the evaporation chamber 10 and the front end ofthe transport pipe 27 from the powder supply source 20. A supersonicnozzle 35 (Laval nozzle) is provided so as to extend from the centerportion of the mixing part 34. On the outer periphery of each transportpipe (17, 27) on the side by the mixing part 34, a not shown coil heatermay be provided to enable heating.

When nanoparticles are produced in the above evaporation chamber 10, thepowder is set in the powder supply source 20, and the interior of thefilm forming chamber 30 is evacuated by operation of the vacuum pump V3,a flow of gas occurs due to a pressure difference between theevaporation chamber 10 and powder supply source 20 and the film formingchamber 30. The nanoparticles and powder are transported together withthe inert gas through the transport pipes to the film forming chamber30.

A first fluid containing nanoparticles and a second fluid containing apowder are mixed in the mixing part 34 and sprayed from the supersonicnozzle (Laval nozzle) 35 attached to the center portion of the mixingpart 34 as a supersonic gas stream (stream of supersonic free jet) Jtoward the substrate for film formation 33 in the film forming chamber30.

The supersonic nozzle 35 is designed based on one-dimensional ortwo-dimensional compressible fluid dynamics in accordance with the typeand composition of the gas and an exhaust capability of the film formingchamber and is connected to the front end of the transport pipe orformed integrally with the front end portion of the transport pipe.Specifically, it is a reduced/extended diameter tube obtained bychanging the diameter of the inside of the nozzle and can raise the gasstream induced due to a pressure difference between the evaporationchamber and the film forming chamber up to as supersonic speed of forexample Mach 1.2 or more.

The nanoparticles and powder are for example accelerated up to asupersonic speed of about Mach 3.6 by the supersonic nozzle 35, ride thesupersonic gas stream, are sprayed toward the substrate for filmformation 33 in the film forming chamber 30, and are deposited on thesubstrate for film formation 33 (physical vapor deposition).

Next, the heating part 16 for heating the evaporation source material 15will be explained.

FIG. 2 is a view showing an arc torch configuring part of the physicalvapor deposition apparatus according to the present embodiment.

In the present embodiment, the heating part 16 uses an arc torch 50 toevaporate the evaporation source material 15.

As shown in FIG. 2, the arc torch 50 has a torch electrode 51 at itsfront end portion. It may have a not shown torch electrode holder aswell. For the torch electrode 51, use can be made of for exampletungsten, stainless steel, or another metal. Further, the current whichis run to the torch electrode 51 is a DC current, DC pulse current, ACcurrent, AC pulse current etc. It is preferably a DC current.

Further, the evaporation source material 15 is made an anode, the torchelectrode 51 is made a cathode, for example a DC current is run to thetwo electrodes to cause discharge, the evaporation source material 15 isheated and evaporated by the generated arc, and fine particles havingsizes of the nanometer order (hereinafter, also referred to as“nanoparticles”) are obtained from atoms evaporated from the evaporationsource material 15.

In the present embodiment, as the heating part 16, the arc torch 50 wasexplained. However, the part is not limited to this. For example, it isalso possible to use a plasma torch to generate plasma and thereby heatthe evaporation source material 15. Further, other than this, it ispossible to use a heating device able to heat and evaporate theevaporation source material 15.

Next, a mixing part 34 will be explained.

The mixing part 34 is coupled with the transport pipe 17 and thetransport pipe 27. In the mixing part 34, the first fluid which istransported from the transport pipe 17 and contains nanoparticles andthe second fluid which is transported from the transport pipe 27 andcontains the powder are mixed.

The mixing part 34 may be a mixing device able to uniformly mix thefirst fluid and the second fluid. The structure is not particularlylimited. For example, it may be a mixing device performing mixing byutilizing an oscillation phenomenon of coaxial impinging jets shown inFIG. 3 as well.

In FIG. 3, a disk-state first mixing nozzle 70 having a substantiallyrectangular shaped first extrusion port 71 and a disk-state secondmixing nozzle 80 having a substantially rectangular shaped secondextrusion port 81 are connected so as to be bridged by a pair ofpartition plates (90, 91).

A space between the first extrusion port 71 and the second extrusionport 81 becomes a mixing region MR for mixing the first jet of the firstfluid and the second jet of the second fluid.

The first mixing nozzle 70, second mixing nozzle 80, and a pair ofpartition plates (90, 91) are for example integrally formed. They areformed from for example brass, stainless steel, or another material byusing a wire cut electrodischarge machine equipped with NC or the like.Alternatively, for example, ones formed for parts may be assembled aswell.

The shapes of the first extrusion port 71 and second extrusion port 81preferably become ones so that or example the lengths of the short sidesare up to about several millimeters, the lengths of the long sides areabout several to ten plus millimeters, and aspect ratios of the lengthsof the short sides and the lengths of the long sides are 4 to 6.

Further, the inter-nozzle distance between the first extrusion port 71of the first mixing nozzle 70 and the second extrusion port 81 of thesecond mixing nozzle 80 is preferably for example a distance of 4 to 35times the lengths of the short sides of the substantially rectangularshapes of the first extrusion port 71 and second extrusion port 81.

For example, the lengths of the short sides of the substantiallyrectangular shapes of the first extrusion port 71 and second extrusionport 81 are about 1 mm, the lengths of the long sides are about 4 mm,the aspect ratios are 4, and the inter-nozzle distance is 16 mm.

Further, a pair or partition plates (90, 91) are provided so that thedistance between the two is substantially equal to the lengths of thelong sides of the substantially rectangular shapes of the firstextrusion port 71 and second extrusion port 81.

For example, a first fluid supply tube T1 is connected to the surface ofthe first mixing nozzle 70 on the side opposite to the mixing region MR.On the other hand, a second fluid supply tube T2 is connected to thesurface of the second mixing nozzle 80 on the side opposite to themixing region MR.

Here, the first fluid containing nanoparticles is supplied from thefirst fluid supply tube T1, and the second fluid containing the powderis supplied from the second fluid supply tube T2. The first fluidbecomes a first jet 72 and is sprayed from the first extrusion port 71to the mixing region MR. Further, the second fluid becomes a second jet82 and is sprayed from the second extrusion port 81 to the mixing regionMR. The first fluid and second fluid are mixed in the mixing region MRdue to the oscillation phenomenon of coaxial impinging jets.

The mixed fluids (94, 95) begin to flow from opening portions (92, 93)facing the mixing region MR to the outside of the mixing region MR.Further, they flow as for example, a merged fluid 96, to the supersonicnozzle.

Here, as pressures of the fluids supplied by the first fluid supply tubeT1 and second fluid supply tube T2 and the pressure of the mixing regionbefore spraying the fluids, for example, pressures of the fluidssupplied by the first fluid supply tube T1 and the second fluid supplytube T2 are set to 60 to 90 kPa, the pressure of the mixing regionbefore spraying the fluids is set to 0.5 to 2 kPa, and a pressure ratiobetween the upstream and the downstream sides of the spray port is setto for example about 45.

It is possible to confirm the situation of mixing of the first fluid andsecond fluid described above by observing, for example, vibration ofpressure in the mixing region of the mixing part.

The mixing part 34 is not limited to a mixing device utilizing theoscillation phenomenon of the coaxial impinging jets, but may be amixing device able to uniformly mix nanoparticles and a powder. Forexample, it may be a for example Y-shaped fluid mixing device or othermixing device mechanically controlling inflow of fluid into a takeoutport by using electric energy from the outside.

Below, a physical vapor deposition method in the present embodimentaccording to the present invention will be explained.

FIG. 4 is a flow chart of the physical vapor deposition method in thepresent embodiment according to the present invention.

Fine particles (nanoparticles) are produced from the evaporation sourcematerial (ST10).

The crucible 14 is provided in the evaporation chamber 10, while theevaporation source material 15 is charged in this. Then, in the vicinityof the evaporation source material 15, the heating part 16 comprised ofan arc torch is provided. By making this crucible 14 an anode electrodeand making the arc torch a cathode electrode and running a DC current,an arc is generated due to discharge between the two electrodes. Theevaporation source material 15 is evaporated by that heat. Byevaporation of the evaporation source material 15, the evaporationsource material 15 becomes atoms, and nanoparticles are generated fromthese atoms.

Next, the fine particles (nanoparticles) and powder are mixed (ST20).

The nanoparticles produced at step ST10 are transported from the insideof the evaporation chamber through the transport pipe 17 to the mixingpart 34. Further, the powder supply source 20 contains the powder. Thepowder is stirred up in the vessel by for example making the vessel ofthe powder supply source 20 vibrate.

Then, the stirred up powder passes through the transport pipe 27 and istransported to the mixing part 34. The nanoparticles and powdertransported to the mixing part 34 are mixed in the mixing part 34.

Next, the fine particles (nanoparticles) and powder are deposited on thesubstrate for film formation to form a film (ST30).

The gas of the mixture of the nanoparticles and powder, i.e., thenanoparticles and powder mixed in the mixing part 34, are sprayed fromthe supersonic nozzle provided in the center portion of the mixing part34 into the film forming chamber 30. At this time, the interior of thefilm forming chamber 30 is an ultra-high vacuum atmosphere. Therefore,these are sprayed from the supersonic nozzle 35 due to the pressuredifference between the mixing part 34 and the film forming chamber 30.The sprayed gas impinges the substrate for film formation 33, whereuponthe nanoparticles and powder are deposited on the substrate for filmformation 33 to form a film.

Next, a dispersion film manufactured by the physical vapor depositionapparatus and the physical vapor deposition method in the presentembodiment will be explained.

FIG. 5 is a cross-sectional view showing a cross-section of a dispersionfilm manufactured by the physical vapor deposition apparatus andphysical vapor deposition method in the present embodiment.

As shown in FIG. 5, the dispersion film manufactured by the physicalvapor deposition apparatus in the present embodiment is comprised of apowdery material comprised of the powder 100 and a material of fineparticles performing a role as a binder comprised of a fine particlematerial film 101.

In the present embodiment, as the fine particles produced from theevaporation source material 15, use can be made of for example a metal,while as the powder-state material, for example a ceramic can be used.

As the metal of the evaporation source material 15, there can bementioned for example Ti, Al, Cr, Fe, Ni, Cu, etc. As the powder-statematerial, there can be mentioned, for example, hydroxyapatite(Ca10(PO4)6(OH)2), molybdenum disulfide (MoS2), titanium oxide (TiO2),titanium nitride (TiN), chromium nitride (CrN), silicon carbide (SiC),boron nitride (BN), diamond-like carbon (DLC), carbon nanotubes, etc.

Here, when the powder 100 is a ceramic, if it is used solo to form afilm, the strength of the film becomes high, but there is thepossibility of the film exhibiting a fragile nature. For this reason, itis possible to mix it with fine particles of metal to form a film andthereby make the metal perform the role of a binder and form a filmhaving a strength of the ceramic and having a lowered fragile nature.For example, a dispersion film formed by dispersion of hydroxyapatite(Ca10(PO4)6(OH)2) in a metal film has a higher bioaffinity than metal,so can be utilized as a bone substitute.

An explanation was given on the dispersion film manufactured in thepresent embodiment by using a metal as fine particles produced from theevaporation source material 15 and using a ceramic as the powder-statematerial, but the invention is not limited to these. A film can beformed by using various materials which can be deposited by physicalvapor deposition by using the physical vapor deposition apparatus of thepresent invention.

According to the physical vapor deposition apparatus and method of thepresent embodiment, a substance which is hard to form into fineparticles even when it is heated by plasma, arc discharge, or the likecan be processed to form a film.

Further, according to the physical vapor deposition apparatus and methodof the present embodiment, a film can be formed by mixing a substance,which would exhibit brittleness if forming a film solo, with anothersubstance.

Further, according to the physical vapor deposition apparatus and methodof the present embodiment, when forming a film by mixing a plurality ofmaterials, the film can be formed without using a plurality of vacuumvessels and heating devices.

Second Embodiment

A physical vapor deposition apparatus and method of the presentembodiment will be explained next.

A dispersion film formed by the physical vapor deposition apparatus andmethod according to the present embodiment has substantially the sameconfiguration as that of the first embodiment shown in FIG. 5.

FIG. 6 is a schematic view of the configuration of an SFJ-PVD apparatusas the physical vapor deposition apparatus according to the presentembodiment described above.

The SFJ-PVD apparatus of the present embodiment is provided with anevaporation chamber 10, a hydroxyapatite particle or other powder supplysource 20, and a vacuum chamber for forming a film comprised of a filmforming chamber 30.

In the evaporation chamber 10, an exhaust pipe 11 which is connected toa vacuum pump VP1 is provided. The interior of the evaporation chamber10 is evacuated by operation of the vacuum pump V1 and is made anultra-high vacuum atmosphere of for example about 10-10 Torr. Further,according to need, to the evaporation chamber 10, He, Ar, N2, or anotherinert gas is supplied from a gas supply source 13 provided via a massflow controller 12 with a predetermined flow rate. The interior of theevaporation chamber 10 is made a predetermined pressure a atmosphere.Alternatively, the interior may be made an air atmosphere.

A copper crucible 14 which is cooled by water is provided in theevaporation chamber 10. An evaporation source material 15 of a metalwhich forms a metal film is charged in this. A heating part 16 such asan arc torch or plasma torch is provided in the vicinity of theevaporation source material 15. The evaporation source material 15 isheated by the heating part 15 to evaporate, whereby fine particleshaving sizes of nanometer order (nanoparticles) are obtained from atomsevaporated from the evaporation source material 15.

As the metal which becomes the evaporation source material, for example,titanium can be preferably used.

The obtained fine particles (nanoparticles) are transported togetherwith the inert gas it the evaporation chamber 10 to the film formingchamber 30 through the transport pipe 17.

In the film forming chamber 30, an exhaust pipe 31 connected to a vacuumpump VP3 is provided. The interior the film forming chamber 30 isevacuated by operation of the vacuum pump V3 and is made an ultra-highvacuum atmosphere of for example about 10-10 Torr.

A supersonic nozzle (Laval nozzle) 36 is provided at the front end ofthe transport pipe 17 from the evaporation chamber 10. A not shown coilheater may also be provided at the outer periphery of the transport pipe17 to make enable heating.

Between the above evaporation chamber 10 and film forming chamber 30, aflow of gas occurs due to a pressure difference, so the fine particles(nanoparticles) are transported together with the inert gas through thetransport pipe 17 to the film forming chamber 30 and are sprayed as asupersonic gas stream (stream of supersonic free jet) J1 from thesupersonic nozzle 36 attached to the front end of the transport pipe 17into the film forming chamber 30 toward the substrate for film formation33.

On the other hand, the powder supply source 20 contains hydroxyapatiteparticles or other powder. The pressure in the vessel configuring thepowder supply source 20 is not particularly limited, but preferably isthe air atmosphere from the viewpoint of operability.

When hydroxyapatite particles are used, use can be made of commerciallyavailable ones. The particle size of the hydroxyapatite particles is forexample tens of micrometers or less, preferably about 0.1 to 10 μm. Forexample, the particle size distribution is about 0.7 to 3 μm. Further,preferably use is made of particles having a hexagonal crystalstructure.

For example, by making the vessel of the powder supply source 20 or thelike vibrate, the powder-state powder is stirred up in the vessel. Thestirred up powder is transported together with the inert gas in thevessel through the transport pipe 27 to the film forming chamber 30.

Between the above powder supply source 20 and film forming chamber 30, aflow of gas occurs due to a pressure difference, so the powder istransported together with the inert gas through the transport pipe 27 tothe film forming chamber 30 and is sprayed as a supersonic gas stream(stream of supersonic free jet) J2 from the supersonic nozzle 37attached to the front end of the transport pipe 27 into the film formingchamber 30 toward the substrate for film formation 33.

In the film forming chamber 30, a stage driven in the X-Y direction isprovided, a substrate holder 32 having an electrical resistance heatingsystem is connected to this stage, and the substrate 33 for filmformation is fixed. The temperature of the substrate 33 is measured by anot shown thermocouple at a point close to the film forming region ofthe substrate 33 and is fed back to the electrical resistance heatingsystem so as to enable the temperature to be controlled.

The substrate for film formation is not particularly limited, but usecan be made of for example a pure titanium sheet (JIS grade 1 or 2),A1050 aluminum alloy sheet, SUS304 stainless steel sheet, etc. Thesubstrate for film formation is preferably used after cleansing bysupersonic waves in acetone before being set in the film formingchamber.

Further, the film forming region of the substrate is set to for example5 to 7 mm square.

The supersonic nozzles (36, 37) are designed based on theone-dimensional or two-dimensional compressible fluid dynamics inaccordance with the type and composition of the gas and the exhaustcapability of the film forming chamber and are connected to the frontends of the transport pipes (17, 27) or formed integrally with the frontend portions of the transport pipes.

The fine particles (nanoparticles) are for example accelerated up to asupersonic speed of about Mach 4.2 by the supersonic nozzle 36, ride thesupersonic gas stream J1, are sprayed into the film forming chamber 30,and are deposited on the substrate for film formation 33 (physical vapordeposition).

The powder is for example accelerated up to a supersonic speed of aboutMach 4.2 by the supersonic nozzle 37, rides the supersonic gas stream52, is sprayed into the film forming chamber 30, and is deposited on thesubstrate for film formation 33 (physical vapor deposition).

As described above, a dispersion film having a structure as shown inFIG. 5 can be formed on the substrate 33.

The deposition of the metal particles and the deposition of the powderdescribed above may be carried out simultaneously, sequentially, oralternately.

Below, a physical vapor deposition method in the present embodimentaccording to the present invention will be, explained.

FIG. 7 is a flow chart of the physical vapor deposition method in thepresent embodiment according to the present invention.

Fine particles (nanoparticles) are produced from the evaporation sourcematerial (ST10).

The crucible 14 is provided in the evaporation chamber 10, while theevaporation source material 15 is charged in this. Then, in the vicinityof the evaporation source material 15, the heating part 16 comprised ofan arc torch is provided. By making this crucible 14 an anode electrodeand making the arc torch a cathode electrode and running a DC current,an arc is generated due to discharge between the two electrodes. Theevaporation source material 15 is evaporated by that heat. Byevaporation of the evaporation source material 15, the evaporationsource material 15 becomes atoms, and nanoparticles are generated fromthese atoms.

Next, the fine particles (nanoparticles) and the powder are sprayed fromthe supersonic nozzles (ST21).

The gas which was produced at step ST10 and contains nanoparticles istransported from the inside of the evaporation chamber by the transportpipe 17 and is sprayed from the supersonic nozzle 36 provided at thefront end of the transport pipe 17 into the film forming chamber 30 dueto the pressure difference between the film forming chamber 30 having anultra-high vacuum atmosphere and the transport pipe 17.

Further, the powder supply source 20 contains the powder. The powder isstirred up in the vessel by for example making the vessel of the powdersupply source 20 vibrate. The gas containing the stirred up powder istransported from the powder supply source 20 by the transport pipe 27and is sprayed from the supersonic nozzle 37 provided on the front endof the transport pipe 27 into the film forming chamber 30 due to thepressure difference between the film forming chamber 30 and thetransport pipe 27.

Next, the fine particles (nanoparticles) and powder are deposited on thesubstrate for film formation (ST30).

The gas containing nanoparticles and the gas containing a powder sprayedas described above impinge upon the substrate for film formation 33,whereby a film of the nanoparticles and powder is formed on thesubstrate for film formation 33.

According to the physical vapor deposition apparatus and method of thepresent embodiment, a substance which is hard to form into fineparticles even when it is heated by plasma, arc discharge, or the likecan be processed to form a film.

Further, according to the physical vapor deposition apparatus and methodof the present embodiment, a film can be formed by mixing a substance,which would exhibit brittleness if forming a film solo, with anothersubstance.

Further, according to the physical vapor deposition apparatus and methodof the present embodiment, when forming a film by mixing a plurality ofmaterials, the film can be formed without using a plurality of vacuumvessels and heating devices.

Example 1

By using an SFJ-PVD apparatus shown in FIG. 6, as shown in the hoveembodiment, a titanium film and a hydroxyapatite particle-dispersedtitanium film having hydroxyapatite particles dispersed in titanium filmwere formed on a titanium substrate.

Titanium sheets of 20 mm×20 mm×1 mm (JIS grade 2, 0.20 of Ti, 0.15 ofFe, 0.13 of O, and 0.05 of N; wt %) were used as the substrates. A 5 mmsquare was refined as the film forming region. All substrates werecleansed by supersonic waves in acetone before being set into the filmforming chamber. The substrate temperature at the time of the filmformation was controlled to 423K.

Further, pure titanium was used as the evaporation source of theevaporation chamber, the internal portion of the evaporation chamber wasmade an He atmosphere of 80 kPa, and titanium particles were produced byarc plasma. The temperature of the supersonic nozzle for placing thetitanium particles on the supersonic gas stream and spraying them wascontrolled to 873K.

In the powder supply source, hydroxyapatite particles having a particlesize distribution of 0.7 to 3 μm (ECCERA Co., Ltd., 36% of Ca, 17% of P,690 mg of Mg, 760 mg of Na, 16 mg of K, 15 mg of Fe, 9.2 ppm of Zn, 90ppm of Ba) were contained, He was used as a carrier gas, the carrier asgas flow rate was controlled to 0 to 4.25 SLM, and the vibration appliedto the powder supply source was set to 0 to 1200 rpm.

The thickness of the obtained hydroxyapatite particle-dispersed titaniumfilm was about 50 to 70 μm, and the composition washydroxyapatite:titanium=about 3:7.

FIG. 8A is an electronic micrograph capturing the entire film formingregion of the hydroxyapatite particle-dispersed titanium film formed asdescribed above, while FIG. 8B is an electron micrograph taken whilemagnifying the surface of the same film.

A state where hydroxyapatite particles are embedded in the metal filmwhich becomes a binder can be observed.

Example 2

FIG. 9A is an X-diffraction profile of a hydroxyapatiteparticle-dispersed titanium film prepared in Example 1. Further, FIG. 9Bis an X-diffraction profile of the powder of hydroxyapatite particles.

As shown in FIG. 9A, peaks indicated by black circles belong tohydroxyapatite (HAp), and peaks indicated by white circles belong tometal titanium (Ti). Namely, the peaks of hydroxyapatite and titaniumwere observed. The film was confirmed to be a dispersion film in whichhydroxyapatite particles were dispersed in a titanium film.

Example 3

An experiment on a titanium substrate dipping a substrate on which ahydroxyapatite-dispersed titanium film formed as described above wasformed in a simulated body fluid was carried out, and the state ofprecipitation of hydroxyapatite was observed.

Here, as the simulated body fluid, use was made of the SBF (simulatedbody fluid) disclosed in the document T. Kokubo and H. Takadama, Howuseful is SBF in predicting in vivo bone bioactivity?, Biomater., 2006,27, p. 2907 to 2915. Namely, it is a solution obtained by dissolvingNaCl, NaHCO3, KCl, K2HPO4.3H2O, MgCl2.6H2O, HCl, CaCl2, Ne2SO4, etc. indistilled ion exchanged water and adjusting it by 1M HCl to 7.4 pH. Ithas a composition near human serum. The temperature of SBF was set to310K, and the dipping time was set to 7 days to 14 days.

FIG. 10A to FIG. 10C are electron micrographs of the surface of thehydroxyapatite particle-dispersed titanium film, in which FIG. 10A showsthe state before dipping in SBF, FIG. 10B shows the state seven daysafter dipping in SBF, and FIG. 10C shows the state 14 days after dippingin SBF. Further, FIG. 10D is a photograph magnifying a portion of FIG.10C.

After dipping for seven days, a situation where the surface of thehydroxyapatite particle-dispersed titanium film became rough andparticles of bone-like apatite were precipitated was observed.

After dipping for 14 days, particles of bone-like apatite further grewand the density became high as well.

The growth of the bone {circumflex over (0 )}like apatite as describedabove is a phenomenon which is not seen in an ordinary titanium film. Itis considered that the hydroxyapatite particle-dispersed titanium filmaccording to the present embodiment provides nucleus-forming sites wherea surface energy for forming the bone-like apatite is low and inducesthe growth of the bone-like apatite.

By forming the hydroxyapatite particle-dispersed metal film according tothe SFJ-PVD method, the following effects can be enjoyed.

(1) A dense hydroxyapatite particle-dispersed metal film free from voidsand cracks can be formed.

(2) By controlling the flow rate etc. of the metal particles andhydroxyapatite particles, a weight ratio between the metal portion andhydroxyapatite particle portion in the hydroxyapatite particle-dispersedmetal film can be selected.

The present invention is not limited to the above explanation.

For example, the fine particles (nanoparticles) are not limited totitanium. The invention can be applied to other metal fine particles orstill other fine particles. Further, the powder is not limited tohydroxyapatite particles. The invention can be applied to other ceramicpowders or still other powders.

Other than those, various modifications are possible within a range notout of the gist of the present invention.

Industrial Applicability

The physical vapor deposition apparatus and method the present inventioncan be applied to a method of mixing metal and other fine particles witha powder to form a film.

The invention claimed is:
 1. A physical vapor deposition method,including: a production step of heating and evaporating an evaporationsource material in a predetermined gas atmosphere or an air atmospherein an evaporation chamber by a heating part which evaporates theevaporation source material to produce fine particles from evaporatedatoms; a stirring step of stirring a powder having a particle size ofnot more than several tens of micrometers in a vessel of a powder supplysource by causing the vessel to vibrate at not more than 1200 rpm; amixing step of transporting the fine particles and the powder from thepowder supply source to a mixing part and mixing the fine particles andthe powder in the mixing part, wherein the transporting is caused by apressure difference between the evaporation chamber and the powdersupply source and a film forming chamber; and a film forming step ofmaking the mixed fine particles and powder ride a supersonic gas streamcreated by a supersonic nozzle connected to the mixing part, depositingthis on the substrate for film formation by physical vapor deposition,and forming a film containing the fine particles and the powder in thefilm forming chamber.
 2. A physical vapor deposition method as set forthin claim 1, wherein the fine particles are made of metal.
 3. A physicalvapor deposition method as set forth in claim 1, wherein the powder ismade of ceramic.
 4. A physical vapor deposition method as set forth inclaim 2, wherein the powder is made of ceramic.